Experiment No

Aim : To determine the acidity of various water samples.

Definition : The capacity of the sample to donate protons or the capacity

of the sample in neutralizing an alkali of known strength.

Causative Factors : Unionized portion of weekly-ionized acids (Carbonic,

tannic, etc) and hydrolyzing salts of Fe3+ and Al3+.
Mineral acids to contribute to the acidity when the pH<
4.5.

Significance : Corrosiveness of the sample.

Expression of the result : Mg/l CaCO3

Titrant : N/50 or 0.02 N NaOH

Indicator : Methyl Orange: End point, Faint Orange: Characteristic
of pH 4.5, Phenolphthalein: End, Pink: Characteristic of
pH 8.3.

Procedure : Add a drop of indicator suitable for the pH of the

sample to 50ml aliquot and titrate against N/50 NaOH
so as to attain an appropriate end point.

Calculation : 1000 ml of 1N NaOH = 50gm CaCO3

1ml of 0.02 = 1 mg CaCO3
Total acidity mg/1 CaCO3 = Vol. of NaOH x 1000
ml of sample

Reactions : Mineral acidity / Organic acid + NaOH
Na-salt of

mineral acid (pH4.5) or Na-salt of Organic acid (pH8.3)

Result :
 Experiment No

Aim :To determine the alkalinity of various water samples.

Definition :The capacity of the sample to donate ‘OH’ ions or accept ‘H+’
ions or to neutralize an acid of know strength.

Theory : Alkalinity of water is its acid neutralizing capacity. It is the

capacity of water to donate OH+ i.e. hydrate ions or accept H-
ions are hydrogen ions. It has the significance in many uses
and treatment of neutral water and waste water. Alkalinity
measurement are used in the interpretation and constant of
water and waste water treatment process.

Causative Factors : Salts of weak acids, weak or strong base, bicarbonates,

carbonates, borates, silicates, phosphates, hydroxides etc.

Significance : Buffering capacity in accommodating H+ and OH- ions in

order to maintain the neutrality.

Standard : Nil
Expression of the : mg/l CaCO3
Result

Titrant : N/50 of 0.02 N H2SO4

Indicator : Phenolphthalein: End Point – Red to colorless. Characteristic
of 8.3 pH.
Methyl orange: End point – Yellow to Orange. Characteristic
of 4.5 pH.

Procedure : Take 50 ml of given sample in a conical flasks. Add 2-3

 drops of phenolphthalein indicator and titrate with 0.02 N
H2SO4 till the colour changes to colorless solution. This is
the ‘P’ end point indicating pH 8.3. Note the burette
reading.( If the pink colour does not appears after addition of
phenolphthalein indicator , the ‘ P’ end point is absent. In this
case, add methyl orange indicator directly and get it complete).
Now add 2-3 drops of methyl orange indicator to the same sample
and titrate with 0.02 N H2SO4 till the yellow colour changes to
orange i.e. pH 4.5 indicating ‘ T ’ end point .Note the total
volume of H2SO4 used.
.
1ml of 1N H2SO4 = 50 mg CaCo3
... 1ml of 0.02 N H2SO4 =1mg CaCo3

Formula:
{ml of H2SO4(0.02N) required
to get ‘P’ end pt. x 1000 }
Phenolphthalein Alkalinity or ‘P’ alkalinity (mg/l CaCo3) =
ml of water sample

{ml of H2SO4(0.02N) required

to get ‘T’ end pt. x 1000 }
Methyl orange alkalinity or
total alkalinity (T) (mg/l CaCo3) =
ml of water sample
Measurement of Individual Alkalinities:

SN Result of OH-alkalinity CO3-2 alkalinity HCO3- alkalinity

Titration mg/l CaCO3 mg/l CaCO3 mg/l CaCO3
1 P=0 0 0 T
2 P<1/2 .T 0 2P T-2P
3 P=1/2 .T 0 2P 0
4 P>1/2 .T 2P-T 2(T-P) 0
5 P=T T 0 0

Reactions:

OH- + H+ --
H2O Phenolphthalein end pt. PH = 10

CO3 2-+ H+ --
HCO3 Phenolphthalein end pt. PH = 8.3
HCO3+ H+ --
H2CO3 Methyl Orange end pt. PH = 4.5
H2O + CO2 --
H2CO3 PH = 4.5pH
+ -
H2 CO3--
H + HCO3 PH = 4.5 to 8.3
(Conjugate base exhibit alkali as well as acid characteristics)
HCO3- --
H++ CO3 2- PH = 8.3 to 10 pH
Or
2-
2HCO3 --
CO3 + H2O + CO2 pH = 10 {Algal action during
Photosynthesis boilers
-
CO3 + H2O --
CO2 + 2OH

Observation Table:

S.N Initial Burette reading Final Burette reading Average value

1
2
3

Calculations of ‘ P’ and ‘ T ’ alkalinity of the given samples

S.N. ‘P’ alkalinity ‘ T ‘ alkalinity

Result:

Conclusion :
 Experiment No

Aim : To determine the chloride content (Avgentometric method) in the given

water samples.

Theory : : Chloride in the form of chloride Cl – ions, is one of the major inorganic
anions in water and waste water. The chloride concentration is higher in
the waste water than the raw water because of sodium chloride ( NaCl) is
a common ingredient of diet and passes unchanged through the
digestive system. At the sea coast, chloride may be present in high
concentration because of leakage of salt water into the sewage system. It
may be also increased by industrial process. High chloride content may
harm metal pipes and structures as well as growing plants.

Principle : In neutral or slightly alkaline solution K2CrO4 indicates the end of silver
chloride gets quantitatively precipitated before red silver chromate is
formed.

Reagents : i) Chloride free water: Demonized water

ii) K2CrO4 indicator: Dissolve 50 gm in distilled water. Add AgNO3
solution till a definite red precipitation is formed. Allow to stand for 12
hours filter. Dilute the filtrate to 1 liter D.W.
iii) Standard AgNO3 (0.0141 N): Dissolve 2.395 gm in distilled water and
dilute to 1 Liter. 1ml of standard silver nitrate (0.0141 N) is equivalent to
500µg Cl-
iv) Standard NaCl (0.0141 N): Dissolve 824.1 mg water and dilute to 1 lit.
1ml of this solution is equivalent to 500µg Cl-.
Procedure: : i) Use 100ml or a suitable aliquot diluted to 100ml with distilled water.
ii) If the sample is colored, add 3ml Al(OH)3 wash combines the filtrate
and washing.
iii) Check the pH and adjust it to near neutrality.
iv) If sulphide, sulphite or thiosulphate is present, make the water alkaline
to Phenolphthalein with NaOH. Add 1ml H2O2, stir, neutralize with
H2SO4.
v) Titrate the sample with AgNO3 after adding 1ml K2CrO4 to the sample
till orange red color appears.
vi) Run the blank taking distilled water as the sample.

Calculation :
1000ml of 1N AgNO3 = 35.45gm Cl-
... 1 ml of 0.0141 AgNO3 = 35.45 x 0.0141mg Cl-
= 0.499mg Cl- or say 500µg Cl- or 0.5mg Cl-

Formula :

(A-B) x 0.5 x1000

-
Mg/l Cl =
ml of sample

Where A = ml titrant of sample

B = ml titrant for blankV

Reaction: Cl- + AgNO3 --
AgCl+ NO3 –

K2CrO4 + 2AgNO3 --
Ag2CrO4 + 2KNO3

If pH> 8.3 - Ag (OH) 2, is precipitated,

If pH < 7 – Cr2 O7, is precipitated.
Ksp AgCl = 3 x 10-10, Ksp Ag2CrO4 = 5x 10-12
Observation Table :

S.N Type of sample (A-B) x 0.5 x1000

-
Mg/l Cl =
ml of sample

Result:

Conclusion :
 Experiment No

Aim : To determine the optimum coagulant dose for the removal of maximum
turbidity (generally a residual turbidity of 20 units is preferred) are
generally carried out with the help of Jar test in the given water samples.

Procedure: : Take500 ml of water samples of which the turbidity is predetermined are

placed in several beakers. Different concentrations of coagulant solution
(1 ml of coagulant = 10 mg) are then added to the turbid solution.
Contents of the beakers are then mixed rapidly at a speed of 100 rpm
(flash mixing) for a period of 5 seconds to achieve an intimate contact
between the coagulant and the turbid waters. After the flash mixing,
contents are flocculated at a very low speed of 20-30 rpm (conditioning)
for ½ an hour and afterwards allowed to stand for one hour. The clarified
supernatant is then decanted and analyzed for residual turbidity. Plots the
graph of applied dose of coagulant against residual turbidity and form it
an optimum dose of coagulant giving a residual turbidity of 20 units is
found out.

Reactions: - i) Al2 (SO4)3 H2O
2Al3+ + 3SO4+

4.5 pH 7.5 pH
3+ -
ii) Al + 3OH ------------ Al (OH)2 ------------- H+ + AlO2- + H2 O
---------
---------
+ H2O
4.5pH 7.5pH

iii) Al3+ + Colloid
Al –colloid. De stabilization

iv ) Al2 (SO4)2 + 6H2O
2Al (OH)3 + 3H2SO4+ 3Ca (HCO3)2 + 3H2SO4

3CaSO4 + 6CO2 + 6H2O
= Al2 (SO4)3 + 6H2O + 3Ca (HCO2) + 3HSO
2Al (OH)3 + 3H2SO4
+ 3CaSO4 + 6CO2 + 6H2O
 Residual Turbidity (Units)

Optimum Dose

Alum Dose

Result :

Conclusion :
 Experiment No

Aim : To determine Biochemical oxygen demand ( B.O.D.)of given

water samples
Theory : BOD is the amount of O2 required by microorganism for stabilizing
biologically decomposable organic matter in water sample under
aerobic condition. It is mainly used to determine pollution load of
the waste water, degree of pollution in lake or stream and the
efficiency of waste water treatment system.
Principle : : The method consist of airtight bottle of specified size overflowing
with sample and incubating at specified temperature for five days.
Dissolved oxygen ( D.O.)of blank and sample is measured and
BOD is calculated using the formula. It is necessary to provide
standard condition such as nutrients, pH, temp and mixed group of
organism is seed for determination of BOD. Temperature is
controlled at 20O C. The test is conducted for 5 days as 70 to 80 %
is stabilized during the period.
Apparatus : Specially prepared BOD glass bottles provided with exactly fitting
ground glass stoppers and surrounding well to accommodate 5 ml
of water so as to exclude exchange of gases. BOD incubator
working at 200C.

Reagents :
i) Distilled water of highest purity and thoroughly aerated so
as to saturate with DO at a lowered temp. of 200C.
ii) Phosphate buffer solution – 8.5 gm KH2PO4 , 21.75 gm
K2 HPO4, 33.4 gm Na2 HPO4.
iii) Magnesium sulphate solution–22.5gm MgSO4H2O
dissolved in 1-1 of distilled water.
 iv) Calcium chloride solution – 27.5 gm anhydrous CaCl2
dissolved in 1-1 distilled water.
v) Ferric chloride solution – 0.25 gm FeCl3, 6 H2O in 1-1
distilled water, All other regents are similar to those in Do
measurement.

Preparation of dilution water: Place required amount of aerated distilled water at 200C. Add 1
ml each of phosphate buffer, magnesium sulphate, calcium
chloride and ferric chloride per liter of water, Seed the dilution
water, if necessary by adding 1 to 10 ml of settled sewage (24
to 36 hours old) per liter (seed should not exert more then 0.5
mg/l of depletion of DO in the blank). Seeded dilution water
should be used the day it is prepared..

Dilution Of sample : When the BOD value is expected to be more than 5.0 mg/l,
dilution of the sample is necessary neutralized at pH 7.0. the
sample should be free from residual chlorine. If it contain
chlorine then sodium sulphade should be added . Make several
dilutions of the prepared in DO. Depletion in DO should not be
less than than 2 mg/ L and dissolved oxygen should not be less
than 1 mg/L after 5 days. Generally following dilutions are
suggested
0.1 to 1 % for strong trade waste
1 to 5 % for raw and settle waste / sewage
5 to 25 % for oxidized effluent
25 to 100 % for polluted river water
Procedure for BOD set up : Select a definite volume of sample (less than 300 ml), add to
BOD bottle and fill completely with dilution water. All
concentrations should be in duplicate. Keep one bottle of each
concentrate in the BOD incubator for 5 Days at 200C and subject
the duplicate of that concentration to do determination on the
same day. That will be O – Day do. After 5 days do. Similarly put
one or two bottles for finding out the depletion of DO in blank
(Seeded dilution water only). Find out the difference in
between O day Do and 5 day DO values.

Calculations : 5- BOD mg/l = Initial DO (mg/l) – 5 day DO (mg/l)

Reaction : CnHaObNc + (n+a/4 – b/2 – 3/4C)O2 - CO2 + (a/2 – 3/2C) H2O +

NH3

Result :

Conclusion :
 Experiment No
Aim : To determine the Chemical oxygen demand (COD ) of given sample.
This is determined by refluxing the sample with an excess of potassium
dichromate in a highly acid conditions and estimating by titration the
amount of dichromate used. With a reducing agent like ferrous ammonium
sulphate.
Theory : The COD is used to measure of oxygen equivalent of organic matter contain
of sample i.e. susceptible to oxidation by a strong chemical oxidant. For ex.
Specific source. COD can be related empirically to BOD organic carbon or
organic matter. The test is useful for monitoring and controlled after
correlation has been established. The dichromate reflux method is prefer to
procedure using other oxidants because of superior oxidizing ability,
applicability to wide varieties of samples and each of the manipulation
oxidation of most organic compound is 95 to 100 % of the theoretical value.
Principle : Most types of organic matters are oxidized by the biolling mixtures and
chromic and sulphuric acid . A sample is reflux in strong acid solution with
the known excess amount of potassium dichromate. After digestion the
reaming unreduced K2Cr2O7 is treated with ferrous ammonium sulphate
(FAS )to determine the amount of K2Cr2O7 consumed and oxidasible organic
matter is calculated in term of oxygen equivalent . Mercuric sulphate is
added to remove inference of chlorides. Silver sulphate is added as a catalyst
as it catalyst oxidation of long chain alphatic compounds.
Interference: Chlorides – 1mg/l Cl- exerts 0.23 mg/l of COD. There fore correction as mg/l
Cl- x 0.23 should be applied the COD of Cl- from the total COD. Nitrites
exert COD of 1.1 mg/mgN.
Limitations: Amino nitrogen gets converted to ammonia nitrogen. All organic compounds
with few exceptions (e.g. aromatic hydrocarbons, straight aliphatic
compounds and pyridine) are oxidized by this procedure.
Reagents:
i) Standard potassium dichromate 0.25 N
ii) Conc. H2SO4 (A.R. Grade)
iii) Ferroin Indicator – Dissolve 1.485gm 1-10 phenanthroline monohydrate together
with0.695 gm ferrous sulphate (FeSO4, 7H2O) in distilled water and dilute to 100
ml.
iv) Catalyst – Silver Sulphate ( for 8 straight chain sulphatic compds) mercuric
sulphate (for Cl-).
v) Sulphomic acid – Required only if the interference of NO2 is to be eliminated.
Add 10 mg sulphamic acid/mg NO2 – N if present, in the refluxing flask. (Do not
forget to add in blank also in this case)
Procedure: Place 50 ml sample or aliquot diluted to 50 ml with distilled water in a 300 ml
round bottom refluxing flask with ground glass joint. Add 25 ml K2Cr2O7 and 75
Conc. H2SO4 gently shake. Attach refluxing condenser and reflux the mixture for
2 hr. After refluxing wash the condenser with distilled water. Cool the mixture.
Dilute the mixture with distilled water. Titrate with ferrous ammonium sulphate
(0.25 N) with ferroin indicator till the red colour apprers after the intermediary
green colour
Note: -
1. While refluxing if the colour changes to green discard the mixture
as potassium Dichromate is not sufficient to oxidize the solution.
2. For small volumes i.e. 10, 20, 30, 40 ml of samples, proportionate
reduction of potassium Dichromate & sulphuric acid may done)
Calculation:
COD mg/l = (A-B) N x 8000 / V
Where A = Volume in ml. Ferrous ammonium sulphate for blank
B = Volume in ml. Ferrous ammonium sulphate for Sample
V = Volume of sample
N = Normality of ferrous ammonium sulphate
 Experiment No
Aim : To determine the pH of given samples
Theory : It is the logarithm of the hydrogen ion concentration with a negative sign [pH = -
log (H)+] Water does not show any reaction with acid or alkali when the
dissociation products of it are in equilibrium (HOH
H+ + OH-. H+ = OH- = 10-
7). pH at this point is 7. When (H+) concentration increases, water becomes acidic
and when decreases water becomes alkaline pH scale –
|
| 7
0 acidic 7 Neutral 14 alkaline

Method: The determination shall be carried out either by the electrometric method, using
glass and calomel electrodes or by the indicator method. In case of dispute the
electrometric method shall be considered as the accurate method.
Electrometric pH Measurement: The pH meter is the most widely used electrical method for
finding out the hydrogen ion concentration of a sample. pH is defined as the
logarithm of hydrogen ion concentration with negative sign. In this case a Glass
Electrode and a Reference Electrode are inserted in a solution and the electric
potential or voltage across these electrodes is taken as a measure of the hydrogen
ions in the solution. Reference Electrode is generally the Calomel Electrode.
With ordinary glass electrode pH can be measured in a range of 2 to 10 pH only
as the glass is made up of sodium silicate which gets affected by pH beyond this
range. Special glass electrode called the Universal Glass Electrode can be used to
detect pH in the full range of 0 to 14.
Indicator Method:
Reagents – Series of indicators and buffer solutions are required for this method or an
universal indicator (0.05 g methyl orange, 0.15 g methyl red 0.3 g bromothymol
blue 0.35 of phenolphthalein in one liter of 66% alcohol). Colour changes shown
by universal indicator are as follows-

pH Up to 4 5 6 7 8 9 10 11
3

Colour Red Orange orange yellow yellowish greenish blue violet reddish
- red green blue violet

Indicators
(Individual indicators for different pH ranges)

Sr. Name of Indicator pH Pange Color Change

No.

(1) (2) (3) (3)

i) Thymol blue (acid range) 1.2 to 2.8 Red to yellow

ii) Bromophenol blue. 3.0 to 4.6 Yellow to blue violet.
iii) Bromocresol Green 3.8 to 5.4 Yellow to blue.
iv) Methyl Read. 4.2 to 6.3 Red to yellow
v) Bromocresol Purple 5.2 to 6.8 Yellow to blue violet.
vi) Bromothymol blue 6.0 to 7.6 Yellow to blue
vii) Phenol Red 6.8 to 8.4 Yellow to red
viii) Cresol Red 7.2 to 8.8 Yellow to red
ix) Thymol blue (alkali range) 8.0 to 9.6 Yellow to blue
x) Thymolphthalein 9.3 to 10.5 Colourless to blue
xi) Thymol violet 9.0 to 13.0 Yellow to Green to violet
 Experiment No
Aim : To determine the turbidity of given water samples
Definition: Absorption coefficient of a liquid or it is the expression of the optical
property of a sample which causes light to e scattered and absorbed
rather than transmitted in straight line through the sample.
Causative Factor: Unfaultable or non-settle able suspended matter (Colloidal) e.g. clay, silt,
finely divided inorganic and organic matter or plankton.
Expression of Result : mg/l SiO2 or as turbidity unit (Jackson Candle turbidity unit JTU).
Preparation of Turbid Solution: Mix slowly, with constant stirring 5.00 g of Fuller’s earth,
previously dried and sifted through 75 microns IS sieve, with distilled
water and dilute it to 1000 ml. Agitate intermittent for one hour and then
allow it to stand for 24 hours. Withdraw supernatant liquid without
disturbing the sediment. Evaporate about 50 ml of the supernatant, dry at
105 ± 20C and weigh the residue so as to determine the exact amount of
fuller’s earth present in 50 ml suspension. Prepare turbidity standards with
this standardized stock suspension with distilled water. A drop of saturated
mercuric chloride solution may be added so as to make the suspension
stable. The standards remain stable for three months.
i) Turbid water should be added in the J.C. turbidimeter so as to cause the
image of the flame of a standard candle to just disappear i.e. to become
indistinguishable against the general background illumination when the
flame is observed through the suspension.
ii) In Aplab: Intensity of the lamp is decreased instead of increasing the
suspension quantity.

Result :
 Experiment No

Aim : To determine the hardness of the given water sample

Theory : Originally water hardness was understood to be a measure of the
capacity of water to precipitated soap. Soap is precipitated chiefly
by the calcium and magnesium ions presents and other polyvalent
cations may also presipate soap, buy they obtain in complex form,
frequently with organic constituents and their role in water
hardness may be minimal and difficult to define. Hence the total
hardness is define as the sum of calcium and magnesium
concentration, both express as Calcium carbonate in mg / L
Principle : Ethylene diamine Tetraacetic acid ( EDTA) and its calcium salt from
a chelated soluble complex when added to the solution of certain
metal cations. If the dye such as Erichrome Black T is added to an
aqueous solution containing calcium and magnesium ions at pH of
10 +- 0.1 , then solution become wine red. If EDTA is added as a
tritant , then calcium and magnesium will be complexed and when
all calcium and magnesium has been complexed , the solution turn
from blue to wine red making the end point of titration. At pH
+2
higher than 10 i.e. around 12, magnesium ions ( Mg ) gets
precipited and only calcium ions remains in the solution. At this
stage if ammonium purported is added it is thenform pink colour.
+2
When EDTA titrate is added, Ca gets complexed and hence
there is a colour change from pink to purple

Causative Factor : Divalent metallization, e.g., Ca2+, Mg2+, Fe2+, Sr2+ etc.

Hardness : Total (Ca2+ + Mg2+) Hardness or TH and Calcium hardness CaH

Expression of the Result: mg/l CaCO3

Titrant: Disodium salt of Ethylene Diamamine Tetraacetric Acid (EDTA) 0.01
N. Dissolve Commercial grade disodium salt of EDTA – 3.723 g in
one liter of distilled water (1 ml of this solution is equivalent to 1 mg
CaCO3.
Standard Solution : Calcium Carbonate: 1 g anhydrous CaCO3 dissolved in 1+1 HC 1 (just
enough) and add 200 ml distilled water. Boil to expel CO2 Cool and
add Methyl Red indicator and adjust to the intermediate orange color by
adding 3 N NH4 OH or 1+1 HCL, -Dilute to 1 liter.
Indicators: a) CaH – Ammonium purpurate or Murexide Color/Change: Purple
(Original) – Pink – purple or Violet.
b) TH – Eriochrome Black T Color Change: Blue – wine
Red-Blue.
Procedure Take EDTA in a burette. Take 10 ml of Std solution of CaCO3 in a
conical flask. Add few ml of NaOH in it. To increase the pH Add
murexide to it as a oxide as an indicator. Tritrate till the colour changes
from pink to purple.
For Total Hardness : Take 50 ml of sample in a conical flask. Add few ml of buffer solution
to it to maintain pH . Add 2-3 drops of EBT and tritrate with std.
solution EDTA till wine red colour turn blue. Note down the reading.
For Calcium Hardness : Hardness due to magnesium is removed by increseing pH of the sample
more than 10 , so that magnesium ions gets precipited. For this purpose,
add few ml of NaOH to 50 ml sample in the conicasl flask and add
murexide as an indicator. Tritrate with Std. solution EDTA till pink
colour changes from pupple. Note down the reading.
Reactions: NaOH
CaH: Murexide indicator (Purple) + Ca2 (part) -----------
Indicator Cachelate.
PH > 10
2+
Excess Ca + EDTA
EDTA – Ca chelate.
EDTA + Indicator – Cachelate
EDTA – Ca chelate + Indicator (purple)
Buffer
2+ 2+
TH: Eriochrome Black T + [Ca + Mg ] part ---------

± 10
Eriochrome Black T-(Ca + Mg) chelate
2+ 2+
EDTA + Ca + Mg excess
EDTA – Ca + Mg chelate
EDTA + Eriochrome Black T – Ca + Mg chelate
EDTA
(Ca+Mg) chelate + Eriochrome Black T (Blue)
TH – CaH = MgH
Result :
 Experiment No
Aim : To determine the Available Chlorine and Residual Chlorine in a Given Water
Sample
Theory :
Chlorine determination includes:
a) Available chlorine in case of chlorine solution, bleaching powder or chlorine tablets.
b) Chlorine demand (assessment of the requirement of the quantity of chlorine to be added).
c) Residual Chlorine- i) Free residual during Break Point chlorination, ii) Total combined
during Break point Chlorination.
Apparatus: Chlorine Determination Kit (Colour Comapatometer)
a) Available Chlorine (Bleaching Powder):
Reagents:
ii) Bleaching powder solution: Make a paste of 1 g. bleaching powder (CaCl, OCL,
H2O) in minimum water and dilute the paste with distilled water to a volume of 100
ml. Take care to see that the paste is transferred tot eh volumetric flask quantitatively.
iii) 0.025N sodium Thisulphate: 6.25 g. Na2S2O3, 5H2O is dissolved in 1 liter of distilled
water.
iv) Glacial acetic acid.
v) Potassium iodide crystals.
vi) 0.1 N potassium iodate solution: 812 mg dissolved in 250 ml. distilled water.
vii) Starch indicator: 5 g soluble starch mixed with little water and ground in a pestle and
mortar so as to prepare a paste. Paste is than transferred quantitatively to 1 liter of
boiling water. Mixture is then allowed to settle overnight and the supernatant is used.

Procedure:
i) Take 10 ml of bleaching powder solution in a conical flask and add to it KI crystals.
Sufficient distilled water and approximately 2 ml of glacial acetic acid mix.
 ii) Titrate the sample till dark amber colored solution turns to pale straw color.
iii) Add starch indicator and Mix.
iv) Titrate till the blue colored starch iodide complex becomes colorless.
v) Prepare reagent blank using distilled water. Note the volume of thiosulphate required.
Calculations:
1 ml of 1 N Thio = 35.45 mg Cl2
1 ml of 0.025 N Thio = 35.45 x 0.025
= 0.88625 or Say 0.89

ml of thio x 0.89 x 100

∴ Percent available= ---------------------------- x (100 in bleaching chlorine ml
of B. P. Solution Powder)
Interference:
Mn, Fe, and NO2 interfere in Iodometric titration. To overcome this interference acetic
acid is used in place of H2SO4 for acidification of the sample.
Reactions:
Ca.OCl.Cl. H2O + 2CH5 COOH
(CH3 COO) 2 Ca + 2H2O+ Cl2
Cl2 + 2 KI
2 KCI + I2
I2 + Starch
Blue colored Starch-iodide complex (Qualitative Test)
I2 + 2Na2 S2 O2
2Nal + Na2 S4 O6 colorless (Qualitative Test)
 Chlorine Demand:
General:
Disinfection is the unit operation which cannot be missed in the treatment plants from the
point of view of supply of safe water. Chlorine either in the form of gas or bleaching powder, is a
universally accepted disinfectant. In addition to destruction of pathogons, chlorination is also
used to achieve oxidation of Fe2+, NH3 Mn +, H2S removal of taste and odour problems and
oxidation of organic compounds in water or waste waters by forming their chloro-derivatives.
In order to have an effective disinfection by chlorine in water treatment, following points
need scientific thinking viz., determination of chlorine dose so as the have residual chlorine of
0.2 mg/l after a contact time of 30 min. These points are very well considered in this concept of
breakpoint chlorination.
Principal:
Bleaching powder or chlorine gas when added to the water reacts with organic matter, if
present, and kills pathogens resulting in the formation of chloroderivatives and free residual
chlorine. The dose which achieves this, leaving behind, o.2 to 0.4 mg/l free residual chlorine can
be taken as chlorine demand of that water for the particular contact period, temp. and PH.

Interference:
Unsaturated organic compounds, Fe2+ Mn2+, NO2, organic nitrogen and NH3 are the main
interfering substances.
These can be eliminated by changing the sequence of regent additions using break point
chlorination.
Apparatus:
Chlorine determination kit (color comparator) to measure residual chlorine.
Reagents:
1. Orthotolidine: Dissolve 1.35 g orthotolidine dihydrochloride in 500 ml distilled
water. Add it to a mixture of 350 ml distilled water + 150 ml Conc. HCl. Store in
a colored bottle.
2. Sod. Arsenite: Dissolve 5 g NaAsO2 and dilute to 1000 ml.
 3. Standard chlorine solution: Prepare chlorine solution from bleaching powder and
determine its strength as described in the test for available chlorine. This solution
has to be prepared freshly.
Procedure:
1. Take identical aliquots of 100ml well water in 12 conical flasks or bottles (stoppered).
2. Add chlorine solution in increasing quantity to the bottles or flasks to result in a
concentration in the range of 0.1 to 3.00 gm/l. Mix well.
3. Allow to stand for predetermined contact period usually 30 to 60 min.

4. Determine the residual chlorine present in each bottle by OT test as described.

5. Plot chlorine residual Vs chlorine added and determines chlorine required at breakpoint.
This will give the chlorine demand of that specific water.
6. This can also be determined by measuring free residual chlorine left after contact period.
The dose where 0.2 mg/l free residual chlorine is left out will give the amount of chlorine
required to disinfect the water.
 ZONE ZONE ZONE
1 2 3

T E OF
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RESIDUAL CHLORINE

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FR
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CR RA N BREAK POINT CHLORINATION
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5 7.5
CHLORINE DOSE
Zone 1 : Major reaction in between Cl2 & NH4+
Zone 2 : Formation of dichloramine & the further
oxidation of it
Zone 3 : Free residual Cl2

Reaction : Cl OH
| |
i) –C = C – + HOCL
- C – C – (unsaturated organic compounds)
| | | |
H H H H

ii) Fe2+Mn2+ /NO2- + HOCL
Fe3+ /Mn3+ /NO3- (Reducing

substances)
iii) H2S + 4Cl2 + 4H2O
H2SO4 + 8HCl (Reducing substances)
iv) NH3 + HOCl
NH2Cl (Monochloramine) + H2O

NH3 + 2HOCl
NHCl2 (Dichloramine) + 2H2O

 NH2Cl + HOCl
NHCl2 + H2O

NH3 + 3HOCl
NCl3* (Trichloramine) + 3H2O

NH2Cl + HOCl
NCl3* + H2O

NH2 + NHCl2 + HOCl
N2O ↑ + 4H2O

NH2Cl + NHCl2
N2* + 3HCl

Formation of chloramines with respect to pH values:

If pH > 8.4, Monochloramines.
If pH is in the range of 4.4 – 5.5, Dichloramines.
If pH < 4.4, Trichloramines
Complete oxidation state of ammonia or the ‘Break Point.’ After this point no more chlorine
demand will be exerted.
At pH in between 5.5 = 8.4 Mono and Dichloramine exist together Relation of these two species
of chloramines is fixed by the pH Value. At pH 7, Monochloramine: Dichloramino = 50: 50.
 Residual Chlorine:
Reagents:
i) Orthotolidine: Weigh 1.35 g. Orthololidine dihydrochloride in 50 ml distilled water.
Add to this mixture 150 ml conc. HCl and make this Vol. to 1 liter. Store the solution
in brown bottle or in the dark.
ii) Sodium arserite solution: Dissolved 0.5 g. Na As O2 (Sodium meta arsenate) in 1000
ml of distilled water. Take care to avoid ingestion since it is toxic.
iii) Copper sulphate solution: Dissolve 1.5 g. copper sulphate in 50 to 60 ml distilled
water, add 1 ml conc-sulphuric acid and make up to 100 ml.
Potassium dichromate solution: Dissolve 0.25 g of potassium dichromate in distilled
water, add 1 ml of conc. Sulfuric acid and make up to 1 liter.
Standard color solution: Measure in the 100 ml. Nessler cylinder the volumes of
copper sulphate solution and potassium dichromate solution so as given in Table and
dilute to 100 ml with distilled water. In column 2 of the table are given amounts of
chlorine to which the color solutions are equivalent.
Procedure:
Use three Nessler cylinders and designate then as cylinders A, B and C. In cylinder a add
1 ml of O-tolidine regent, 100 ml of the sample, mix and add immediately 2 ml of sod. Arsenite
solution, mix
and after 5 seconds, compare the color with standard color solution.
This reaction (FR) represents the total of free residual chlorine and of interfering substances.
In cylinder B, add 2 ml of sodium arsenite solution and 100 ml of the sample mix and add
immediately 1 ml of orihotolidine reagent. Mix and match the color with standard solutions. This
reading (B1) is the blank for interfering substances after 2 min standing. Also allow it to stand for
5 minutes and record the result. This reading (B2) is the blank for interfering substance after 5
minutes standing.
In cylinder ‘C’ add 1 ml of O-tolidine reagent and 100 ml of the sample, mix and after 5
minutes match the color. This reading (TR) gives the total residual chlorine plus interfering
substances.
 NOTE: Use 0.5 ml Orhotolidine for 10 ml. sample
0.75 ml Orhotolidine for 15 ml. sample
TABLE : Standing color solutions for residual chlorine determination

Sr. No. Chlorine Copper Sulphate Solution Potassium Dichromate Solution

Mg/l ml Ml

I 0.01 0 0.8

II 0.02 0 2.1

III 0.03 0 3.2

IV 0.04 0 4.3

V 0.05 0.4 5.5

VI 0.06 0.8 6.6

VII 0.07 1.2 7.5

VIII 0.08 1.5 8.2

IX 0.09 1.7 9.0

X 0.10 1.8 10.0

XI 0.15 1.8 15.0

XII 0.2 1.9 20.0

XIII 0.25 1.9 20.0

XIV 0.30 1.9 30.0

XV 0.35 1.9 34.0

XVI 0.40 2.0 38.0

XVII 0.50 2.0 45.0

XVIII 0.60 2.0 51.0

XIX 0.70 2.0 58.0

XX 0.80 2.0 63.0

 XXI 0.90 2.0 67.0

XXII 1.00 3.0 72.0

Calculation:
a) Free residual chlorine (as Cl) mg/l = FR-B1
b) Total residual chlorine (as Cl) mg/l = TR-B2
c) Combined residual chlorine (as Cl) mg/l = (TR-B2) - (FR-B1)
Range:
The method is applicable up to 5 mg/l of chlorine.
 setting time Settled solids t Dissolved Solid +
(Total solids) -----------
Colloidal or suspended solids
Volatile: organic fraction
Dissolved Solids (filtrate) --
Fixed: Residue after burning
At 6000C for 1 hr.
Filter Settled Water -

Volatile: organic fraction
Suspended Solids --
(Retained on filter paper) Fixed: Residue after burning
At 6000C for 1 hr.
Procedure:
Total Solids:
Pipette out 100 ml of well mixed sample in to the clean dry weighing dish and evaporate
to dryness at 1050C. Cool the weighing dish at R.T. and weigh.
mg of residue x 1000
Total solids mg/1 =
Ml sample.
Fixed residue:
Ignite the residue obtained in total solids determination or volatile solids determination at
550C to 6000C for one hour in the platinum crucible in the muffle furnace. Cool the crucible and
weigh.
Find out the amount of fixed residue in the and contains dissolved
nonvolatile as well as suspended nonvolatile residue. This is known as ignited residue also.
mg of residue x 1000
Ignited residue, mg/1 = ------------------------------------
Ml sample.
Or fixed residue
Volatile residue = Total solids - Ignited residue
Dissolved Solids:
 Pipette out 100 ml of the well mixed sample and filter through a filter paper. Collect the
filtrate in a clear and previously weighed evaporating dish at room temperature and weigh,
mg of residue x 1000
Total dissolved solids mg/1 =
Ml sample.
Suspended matter – It is determined generally indirectly as follows-
Suspended matter mg/ 1 = Total solids mg/1 – Dissolved solids mg/1
If the Glass Fiber filter paper GFC grade (What man make) is available this
determination can be done directly. This paper keeps the consistency not only at 1050C but at
6000C also. While using this filter paper a separate filter assembly known as Hartley’s Filter
assembly is made use of.

2) Sulphate (Turbidimetric Method)

Principle: Barium sulphate is precipitated as Barium sulphate in hydrochloric acid medium with
barium choride, in a near colloidal form. The absorbance of light caused by the barium sulphate
suspension is measured by a nephelometer or colorimeter and the sulphate ion concentration is
determined by using a calibration curve prepared with standard sulphate solution.
Apparatus:
1) Magnetic stirrer
2) Klett summerson colorimeter or spectro photometer
3) Measuring spoon
Reagent:
a) Conditioning reagent – Mix 50 ml glycerol with a solution containing 30 ml conc.
HCL, 300 ml distilled water, 100 ml 95% ethyl alcohol and 75 gm sodium chloride.
 b) Barium chloride crystals ‘AR grade’.
c) Standard Sulphate solution – Prepare by diluting 10.41 ml of the standard 0.02 NH2SO4
to 100 ml with distilled water.
Procedure:
a) Formation of barium sulphate turbidity – Measure 100ml
sample or a suitable aliquot made up to 100ml into a 250ml
Erlenmeyer flask. Add exactly 5 ml conditioning reagent and
mix in the stirring apparatus. While the solution is being
stirred add a spoon full of barium chloride crystals stir
b) Measurements of barium sulphate turbidity – Immediately after the stirring period is
over, pour some of the solution into the absorption cell of the photometer and
measure the absorption at fifth minute. Maximum turbidity is usually achieved within
2 min. and the reading remains constant there after for 3-10 min.
c) Read mg SO4 present in the sample on the calibration curve prepared by standard
solutions,
d) Calculation: mg / l SO42- = mg SO42- x 1000 / ml sample

Conditioning
2-
Reaction - SO4 + BaCl2 Ba SO4 SO4Solution

13) EDTA - Titrimetric Method

Reagent:
i) EDTA Solution – 4 gm disodium dihydrogen ethylene diamine tetra acetic acid
dehydrate are dissolved in one liter of distilled water. Standardize against standard Ba
Cl2 solution.
ii) Buffer – Mix 67.5 gm pure NH4Cl4 with 750 ml NH2OH
(sp. gr. 0.92) and dilute to 1 liter.
iii) Indicator – Eriochrome Black T.
 iv) Ba Cl2 standard – dissolve 2.443 gm Ba Cl2 2H2O in 1 liter, One ml solution = 1mg
CaCO3 or 0.96 mg SO42-.
Producer: Neutralize 100 ml with 1 NHNO3. Boil to expel CO2. Add 10 ml or more if required,
of Ba Cl2 standard solution to the boiling sample and allow cooling. Dilute to 200 ml mix
indicator. Titrate with std. EDTA till blue color appears.
 Experiment No
Aim : To determine the turbidity of given water samples
Definition: Absorption coefficient of a liquid or it is the expression of the optical
property of a sample which causes light to e scattered and absorbed
rather than transmitted in straight line through the sample.
Causative Factor: Unfaultable or non-settle able suspended matter (Colloidal) e.g. clay, silt,
finely divided inorganic and organic matter or plankton.
Expression of Result : mg/l SiO2 or as turbidity unit (Jackson Candle turbidity unit JTU).
Preparation of Turbid Solution: Mix slowly, with constant stirring 5.00 g of Fuller’s earth,
previously dried and sifted through 75 microns IS sieve, with distilled
water and dilute it to 1000 ml. Agitate intermittent for one hour and then
allow it to stand for 24 hours. Withdraw supernatant liquid without
disturbing the sediment. Evaporate about 50 ml of the supernatant, dry at
105 ± 20C and weigh the residue so as to determine the exact amount of
fuller’s earth present in 50 ml suspension. Prepare turbidity standards with
this standardized stock suspension with distilled water. A drop of saturated
mercuric chloride solution may be added so as to make the suspension
stable. The standards remain stable for three months.
iii) Turbid water should be added in the J.C. turbidimeter so as to cause the
image of the flame of a standard candle to just disappear i.e. to become
indistinguishable against the general background illumination when the
flame is observed through the suspension.
iv) In Aplab: Intensity of the lamp is decreased instead of increasing the
suspension quantity.

Result :